Benzanthrone dicarboxylic acid compounds



Patented Jan. 17, 1950 BENZANTHRONE DICARBOXYLIC ACID COMPOUNDS TheodorHolbro, Basel, Paul Sutter, Binningen, and Walter Kern, Sissach,Switzerland, assignors to Ciba Limited, a Swiss firm No Drawing.Application July 19, 1946, Serial No. 684,776. In Switzerland July 27,1945 9 Claims. (Cl. 260276) According to this invention valuable vatdyestuffs are made by causing a benzanthrone dicarboxylic acid which isincapable of internal anhydride formation to react with one or moreamines.

The requirement that the dicarboxylic acids serving as startingmaterials for the present process shall be incapable of internalanhydride formation is fulfilled, for example, when the carboxyl groupsdo not occupy orthoor peri-positions relatively to one another.Otherwise these groups may occupy any desired positions and may be, forexample, substituents in the Bz-nucleus or in the anthraquinone nucleus.As an example there may be mentioned benzanthrone-fi-Bzldicarboxylicacid, and benzanthrone-2:6-dicarboxylic acid.

'The reaction of such benzanthrone carboxylic acids with amines isadvantageously conducted after converting the carboxylic acid groupsinto reactive derivatives of such groups, for example, into acid halidegroups. Thus, two molecular proportions of the same amine or differentamines may be caused to act either simultaneously or in succession upon1 molecular proportion of a benzanthrone carboxylic acid containing twocarboxylic acid groups or on an acid halide thereof, for example, thechloride. As amines there come into consideration, for example,aliphatic, hydroaromatic or aromatic amines, and especially aminescontaining vattable groups, for example at least one carbonyl groupforming part of a ring and, in addition, at least three condensedsix-mcmbered carbon rings. Such amines may be anthraquinone derivativesor they may possess more highly condensed ring systems. amines are, forexample, l-aminol-benzoyl- Such aminoanthraquinone,l-amino-5-benzoylaminoanthraquinone, 1 amino 5 benzoylamino 8-methoxyanthraquinone, l-aminoanthraquinone, lamino-4-methoxyanthraquinone, Lamina-5- methoxyanthraquinone, l-amino 5chloroanthraquinone, l-amino 6 chloroanthraquinone,Z-aminoanthraquinone, an aminopyranthrone, an aminodibenzanthrone, anamino-flavanthrone,

an aminobenzanthrone, an aminoanthanthrone,

fall

It is of advantage to use vattable' compounds which contain, forexample, in ortho-position with respect to the reactive aminogroup, atleast one substituent which is capable of leading to the formation of aheterocyclic ring. Such substituents are, for example, hydroxyl, nitro,mercapto or amino groups, and also'halogen atoms. Depending on theconditions of reaction the formation of an oxazole, thiazoleor'imidazole ring may follow directly upon the reaction of the reactivecarboxylic acid derivative, especially. an acid halide, with or Withoutthe use cfaspecial condensing agent, or if desired this may be broughtabout in a separate operation by a method in itself known. Thus, forexample, oxazoles can be produced from carboxylic acid chlorides andortho hydroxy aminoanthraquinones, for exampleZ-hydroxyamino-l-anthraquinone, accompanied by thesplitting ofLofhydrogen halide and water, or from benzanthrone carboxylic acidchlorides and orthoenitro-aminoanthraquinones (for example,Z-nitro-l-aminoanthraq'uinone) accompanied by the splitting off ofhydrogen halide and nitrous acid or from brom-amino- (for example,1:2-)anthraquinones accompanied by the splitting off of hydrogenchloride and hydrogen bromide.

Thiazoles are obtained, for example, by causing benzanthrone carboxylicacid chlorides to react with ortho-mercapto-aminoanthraquinones, forexample, 1:2- or 2zl-mercapto-amino-anthrae quinones. Finally,imidazoles can be obtained by the reaction of the sam reactivebenzanthrone carboxylic acid derivatives withortho-diaminoanthraquinones or with o-rtho enitro-aminoan- .thraquinoneswith reduction of the nitro group,

or with ortho-halogenaminoanthraquinones, especially those having ahalogen atom in 0t-pUSition, after reaction with ammonia or a primaryamine.

The reaction of the benzanthrone carboxylic acid or its reactivederivative, the isolation of which is in many cases unnecessary, withthe amine containing at least one reactive hydrogen atom isadvantageously carried out by heating the components in a solvent ordiluent, for example, dior tri-chlorobenzene, nitrobenzene, naphthaleneor chloronaphthalene, during which, as stated above, ring closure occursin some cases.

The condensation products obtainable by the process of the invention maybe treated with condensing agents and/or agents capable of introducingsubstituents, whereby further valuable products can be obtained' As suchagents there may be mentioned for example, alkylating agents,

halogens or agents yielding halogen, also acid or alkaline condensingagents, for example, aluminium halides, if desired in presence of atertiary base, such as pyridine, or of potassium chloride or sodiumchloride.

The new products may be purified by crystallization one or more timesfrom organic solvents or by treatment with oxidizing agents, for examplea solution of an alkali hypochlorite, a solution of sodium nitrite in anacid medium or a solution of a perborate. The products can be convertedby known methods into leuco-derivatives, for example, sulfuric acidleuco esters. The products of the invention are valuable vat dyestuffs,which can be used for example as pigments or for dyeing or printinganimal fibers, such as wool and silk, but more especially vegetablefibers for example, cotton, linen, rayon and staple fibers ofregenerated cellulose, and also superpoly-amides. The dyeings and printsproduced therewith poss es 's,'in some cases, excellent fastness towashing, chlorine and boiling in alkali. "There are obtained inparticular, very va uable yel ow dyestuf s.

The following examples illustrate the invention, the parts being byweight unless otherwise stated, the relationship of parts by weight toparts by yolume being the same as that of the ram t9 he liter:

Example 1 15,9 arts 9f bcnzanthrone-fi:Bzl-dicarboxylic acid areconverted into the acid chloride by heat a yellow coloration having astrong yellow-green fluorescence.

Example 2 1'7 .75 parts of benzanthrone-S:Bzl-dicarboxylic acid chlorideare introduced into a solution of 34.2 parts of1-amino-5-benzoylaminoanthraquinone in 1000 parts of dryortho-dichlorobenzene at 150 C. After stirring for 2 hours at thattemperature the reaction is complete. The whole is filtered withsuction, while warm, the filter residue is washed withorthodichlorobenzene and alcohol, and dried. In this manner the samedyestuff as that of Example 1 is obtained.

' The acid chloride used in this example may be prepared in thefollowing manner:

15.9 parts of benz anthrone-G:Bzl-dicarboxylic acid, 320 parts of dryortho-dichlorobenzene, 32 parts of thionyl chloride and 0.1 part ofpyridine are heated to boiling in a reflux apparatus while stirringuntil dissolution is complete and hydrochloric acid is no longerevolved. Upon cooling the resulting benzanthrone-6:Bzl-dicarboxylic acidchloride crystallises. It is separated by filtering with suction, Washedwith ortho.-dichlorobenzene and petroleum ether, and dried. The paleyellow crystals melt at 215 C.

Example 3 The procedure described in Example 1 or 2 is followed, exceptthat the 1-amino-5-benzoylamino-anthraquinone is replaced by one of theamines in the following table, which table also gives the properties ofthe resulting dyestuffs:

Amine:

Dyestuff:

Coloration in sulfuric acid Color of the vet Dyeing on cotton (a)l-amino-anthraquinone (b) Lamino-A-methoxy-anthraquinone (c)lamino-debcnzoyl-aminoanthraquinonc.

(d) 4.-aminoahthra'quinone-l (N) :Z-benzarldone reddish-yellowviolet-brown. l red A greenish-yellow. .do

rcddishwellow. .do... o orange-brown. rcddish-yellow red-brown....blue-green.

ing with 20 parts of thionyl chloride in 1000 parts of drydichlorobenzene. After removing the unconsumed thionyl chloride bydistillation 34.2 parts of lamino-5-benzoylaminoanthraquinone areintroduced at 150 C; After stirring for 2 hours at 150 C. dyestuifformation is complete. The whole is filtered with suction while warm,the filter residue is washed with ortho-dichlorobenzene and alcohol, anddried. The dyestuif of the formula l I It i) O H NH-CO J g o NH-C o-Example 4 17.8 parts of benzanthrone-Z:S-dioarboxylic acid chloride arepoured at G. into a solution of 22.3 parts of l-aminoanthraquinone in1000 parts of dry ortho-dichlorobenzene. After stir ring for two hoursat C. the reaction is complete. The precipitated dyestuff is filteredoff with suction while warm, washed with orthodichlorobenzene andalcohol, and dried. In this manner a yellow powder is obtained, which isillustrated by the formula and which dissolves in concentrated sulfuricacid with orange-yellow coloration and dyes cotton from anolive vatgreenish yellow tints.

The benzanthrone-2:S-dicarboxylic acid chlo- 6 Example 5 "Through thereplacement, in Example 4, of I-zxmino-anthraquinone by other amines,there ar obtained the dyestuffs shown by this table:

Dyestuii:

Amine:

Color in Sun-uric acid Vet color Tint on cotton 1 (a)2-amino-anthraquinone yellow.

(11) lamino-4-benzoylaminoanthraquinone. orange.

() 1-amino-5-benzoylaminoanthraquinone. yellow.

(:1) 1am no -benzoylamino-S-methoxyanthraquinone..- V orange.

(e) 1-ammo-4-methoxyanthraquinone. yellowish brown D (l)s-aminoanthraquinone-l (N): 2-benzacridon (m) 3-amino-lz2(N)-pyridine-anthraquinone ('n) 4-amino-lz9-anthrapyrimil-arnino-7-chloroanthraquinone e .slll.-.

o. greenish yellow.

reddish brown. greenish yellow.

olive-brown.

olive-gray. greenish yellow.

Y yellow-red...

ride used in this example may be produced as follows:

11.64 parts of 2:6-dibromobenzanthrone (of. German Patent No. 471,021)are thoroughly mixed with 6 parts of cuprous cyanide, 2.7 parts ofpyridine and parts of nitrobenzene and then heated in a bomb tube for 12hours to 1'75- 185 C. The reaction product is suction-filtered in thecold state, the filter residue is washed with nitrobenzene and alcohol,boiled with dilute nitric acid, repeatedly suction-filtered, Washed withWater and dried. When recrystallized from nitrobenzene, the thusobtained 2:6-dicyanbenzanthrone is a pale yellowish-brown crystal powderwhich melts at 395-400 C.

25.8 parts of 2:6-dicyanbenzarithrone are dis solved in 355 parts ofconcentrated sulfuric acid, and parts of water are carefully added. The

aponification mixture is heated to -155" 0.

yellow powder which melts at 416 C. with decomposition.

15.9 parts of benzanthrone-Zzs-dicarboxylic acid, 210 parts ofortho-dichlorobenzene, 27 parts of thionyl chloride and 0.1 part ofpyridine are heated to the boil while stirring until dissolution Ewample6 wherein one X means H and the other and CO-NH O A NH-O O-O Example 717.1 parts of 1-amino-5-benzoylamino-anthraquinone. 17.8 parts ofbenzanthrone-GEBzl-dicarboxylic. acid chloride, 11 parts of pyridine and1200 parts of dry nitrobenzene are stirred together at 45-55 C. untilreaction is complete. with all of the starting materials. There followheating to 150 C., the addition of parts of, aniline and stirring for 2hours at ISO-160 C. in order to complete the formation of the dyestufi.The dyestuff, which has formed in several stages; is filtered ofi bysuction while warm, washed with. nitrobenzene and alcohol, and dried. Itis represented by the formula CO-NH o or a mixture of both. It is anorange-brown powder, dissolving in concentrated sulfuric acid with a redcoloration and dyeing cotton from a redbrown vat yellow tints.

Example 8 ill Example!) 4'- parts' of the reaction product from 1molecular proportion of benzanthrone-6zBzl-dicarboxylic acid chlorideand 2 molecular proportions of 1-chloro-2-amino-anthraquinone (obtainedaccording. to the process, explained in Example 2), 4 parts of copperacetate, and 60 parts of aniline are stirred for six hours while boilingunder reflux. When the precipitated dyestuif has cooled off it issuction-filtered, washed with aniline and alcohol, boiled withhydrochloric acid, again suction-filtered, washed with water, and dried.It is a yellow-olive crystalline powder which dissolves in concentratedsulfuric acid with yellow-brown coloration and dyes. cotton from a brownvat in greenish yellow tints. It is presumed to be otthi's constitution:

Example 1 0- Through the reaction of'l molecular proportion ofbenzanthrone-6zBzl-dicarboxylic acid chloride with 2 molecularproportions of 2:3-aminohydroxyanthraquinone by the process described inExample 2, a yellow-brown powder is obtained which dissolves. inconcentrated sulfuric acid with red-brown coloration and dyes cottonfrom a brown vat dull greenish yellow tints. Upon soaping the shadeturns orange brown. The dyestuii isaof this constitution:

2,494,811 9 10 2 parts of this dyestufi are dissolved in 20 parts orangetints. It is presumedto be of the following of sulfuric acid of 100 percent. strength and Constitution: 5 1

heated for minutes to 130-140 0., whereby the 0 color of the solution ischanged to brown with lg C I green fluorescence. When it has cooled off,it is poured onto ice, the precipitated dyestuff is fil I tered off withsuction, washed and dried. It dyes A) cotton from an olive brown vatgreenish yellow 10 tints which are fast to soaping. It is presumed to beof this constitution:

0 N ll Example 11 Ewample 12 At a temperature of 100? C. 17.8 parts ofbenz- 39.9 parts of the dyestufl listed beside the letter anthrone-G:Bzl-dicarboxylic acid chloride are it in the table in Example 5, 34.2parts of l-aminopoured into a solution of 25.6 parts of l-mercapto-5-benzoyl-amino-anthraquinone, 15 parts of so- Z-aminoanthraquinone in1000 parts. of dry tridium carbonate, 15 parts of sodium acetate, 1.5chlcrooenzene. After stirring for two hours at parts of cuprous chlorideand 500 parts of dry 150-160 C. and for another two hours at the boil,nitrobenzene are stirred while being heated to the the precipitateddyestuif is filtered off with sucboil for 15 hours. The precipitatedreaction prod-w time while warm, washed with trichlorobenzene uct isfiltered oil with suction while warm, washed and alcohol and dried. Itis an olive powder which with nitrobenzene and alcohol, boiled withdilute dissolves in concentrated sulfuric acid with a hydrochloric acid,again suction-filtered, washed brown coloration and dyes cotton from aredwith water and dried. Itisablack-brown powder brown vat orange-browntints. which dyes cotton from 'a brown vat red brown The dyestuil may bepurified as follows: tints. It dissolves in concentrated sulfuric acid 2parts of the crude product are reprecipitated with an olive colorationwhich soon turns; violet. from sulfuric acid and suspended in 200 partsof 5 The dyestufi is of this constitution:

C O-HN (I) O NIH-OG- 1; NHO

GOO-NH Water. 20 parts of Javelle water of 14 per cent. 2 parts of thisdyestufl are added to 20 parts of strength are added andthe whole isstirred at sulfuric acid of 96 per cent. strength whereby the the boiluntil the color of the dyestufi does not color of the solution ischanged from olive to viobecome lighter any more. The dyestufi issuclet. After stirring for 5 hours at 20 C. it is poured tion-filtered,washed and dried. 1 The purified onto ice, 0.6 part of sodium-nitrite isadded and dyestufi is a yellow-brown powder which dissolves the whole isstirred for several hours at 05 C. in concentrated sulfuric acid withred-brown col- The dyestufi is then suctioriaflltered, washed withoration and dyes cotton from a red-brown vat in 5 water and made into apastes; It dyes cotton from all a brown vat yellow-brown tints and ispresumed to be of the constitution:

O NH-OC- from aluminum chloride and sulfur dioxide (obtainable byintroducing sulfur dioxide into a mixture of aluminum chloride andsodium chloride).

Example 1 3 18.2 parts of the dyestufi described in Example 4 aredissolved, with the addition. of dlpart of iodine, in 250 parts ofchlorosulfonic acid. 8.4 parts of bromine are added drop by drop at atemperature of -5 C. and the solution is stirred for 24 hours at 0-5" C.and for hours at C. After this,-500 parts of concentrated sulfuric acidare slowly run in, the mixture is poured onto ice, the precipitatedproduct is filtered oif with suction, washed with water and dried. Thebromic dyestuff so obtained dyes cotton from an olivebrown vat greenishyellow tints.

Example 14 0.5 part of the dyestuff of Example 1 or 2 is thoroughlypasted with 4.5 parts by volume of caustic soda solution of 36 B. and100 parts of Water at 5060 C., 1.2 parts of hydrosulfite are added andvatting is carried on for hour at the same temperature. Into a dyebathof 700 parts of water are introduced 1.5 parts by volume of caustic sodasolution of 36 B. and 1 part of hydrosulfite and also the stock vat,parts of cotton are entered, dyeing is carried on for hour at 50-60" C.,the material is unwound, oxidized for A; hour in air, rinsed, acidifiedand soaped at the boil. The cotton is dyed fast yellow tints.

What We claim is:

1. A vat dyestufi of the general formula wherein R1 stands for abenzanthrone radical and wherein R2 and R3 stand for aromatic radicalsat least one of them being the radical of a vattable compound, thegroups CONHR2 and CONH-R3 being attached to ring carbon atoms of thebenzanthrone radical which are separated by at least two ring carbonatoms.

2. A vat dyestuff of the general formula separated by at least two ringcarbon atoms. 3. A vat dyestuif of the general formula wherein R2 and R3stand for radicals of vattable compounds containing the anthraquinoneskeleton, the groups CO--NH--R2 and CONH R3 being attached to ringcarbon atoms of the benzanthrone radical which are separated by at leasttwo ring carbon atoms.

4. A vat dyestuff of the general formula wherein R2 and Rs stand foranthraquinone radicals, the groups -CONH-'R2 and CONH R3 being attachedto ring carbon atoms of the benzanthrone radical which are separated byat least two ring carbon atoms.

5. The vat dyestufi of the formula 6'. The vat dyestufi of the formula7. The vat dyestufi of the formula 9. A vat dyestufi of the generalformula PAUL SUTTER. WALTER KERN.

NH REFERENCES CITED The following references are of record in the fileof this patent:

35 UNITED STATES PATENTS Number Name Date 8. A vat dyestuff of thegeneral formula 2,081,874 Lycan May 25, 1937 2,111,074 Lycan Mar. 15,1938 2,155,360 Lulek et a1. Apr. 18, 1939 40 2,459,941 Holbro et a1 Jan.25, 1949 FOREIGN PATENTS Number Country Date RFNH 251,480 Germany Oct.3, 1912 wherein R2 and Rs stand for anthraquinone radicals.

N H I? o RaNHCO- l -00-1- n1 25 wherein R2 and Rs stand foranthraquinone radicals. NH-CO- THEODOR HOLBRO.

Certificate of Correction Patent No. 2,494,811 January 17, 1950 THEODORHOLBRO ET AL.

It is hereby certified that errors appear in the printed specificationof the above numbered patent requiring correction as follows:

Column 1, line 46, after aminoanthrimide strike out the period andinsert instead a comma; column 7, line 42, for anthorne read anthrone;lines 55 to 62, mclusive, for that portion of the formula reading column8, last formula, left hand portion thereof, for

o 0 ll 1% column 12, last formula, for that portion reading -0 O-NH(JO-NH read and that the said Letters Patent should be read with thesecorrections therein that the same may conform to the record of the casein the Patent Oflice.

Signed and sealed this 6th day of J mm, A. D. 1950.

[smnl THOMAS F. MURPHY,

Assistant Gammz'ssioner of Patents.

1. A VAT DYESTUFF OF THE GENERAL FORMULA